Wang Chengdong, Xiao Guanlin, Guo Tao, Ding Yalan, Wu Xiaojin, Loh Teck-Peng
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials , Nanjing Tech University , Nanjing 211816 , People's Republic of China.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences , Nanyang Technological University , Singapore 637616 , Republic of Singapore.
J Am Chem Soc. 2018 Aug 1;140(30):9332-9336. doi: 10.1021/jacs.8b03619. Epub 2018 Jun 22.
A general Pd-catalyzed intermolecular reductive Heck reaction of both terminal and internal unactivated aliphatic alkenes has been first developed. This method affords γ- and δ-arylated alkyl carboxylic acid derivatives in high yields with complete anti-Markovnikov selectivity. Notably, the coupling process is stereoretentive for the alkyl chain. Mechanistically, alkyl palladacycle intermediates stabilized by directing group and ligand, hydride species multigenerated from PS/TFA reductant, are two key factors that successfully promote the reaction and regioselectivity.
首次开发了一种通用的钯催化的末端和内式未活化脂肪族烯烃的分子间还原Heck反应。该方法以高产率提供γ-和δ-芳基化烷基羧酸衍生物，并具有完全的反马氏选择性。值得注意的是，偶联过程对烷基链具有立体保持性。从机理上讲，由导向基团和配体稳定的烷基钯环中间体以及由PS/TFA还原剂多步生成的氢化物物种是成功促进反应和区域选择性的两个关键因素。
